CN114665096B - Graphene composite conductive slurry for battery and preparation method and application thereof - Google Patents
Graphene composite conductive slurry for battery and preparation method and application thereof Download PDFInfo
- Publication number
- CN114665096B CN114665096B CN202210359191.5A CN202210359191A CN114665096B CN 114665096 B CN114665096 B CN 114665096B CN 202210359191 A CN202210359191 A CN 202210359191A CN 114665096 B CN114665096 B CN 114665096B
- Authority
- CN
- China
- Prior art keywords
- graphene
- slurry
- preparation
- conductive
- conductive paste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses graphene composite conductive slurry for a battery and a preparation method and application thereof, wherein the conductive slurry comprises the following preparation raw materials: a conductive agent and a dispersant; the conductive agent comprises the following preparation raw materials: carbon quantum dots, amino modified graphene and carboxylated carbon nanotubes; wherein the mass ratio of the carbon quantum dots, the amino modified graphene and the carboxylated carbon nanotubes is 1:1 to 2: 1-2; in the conductive paste, a carboxyl carbon nano tube, amino modified graphene and carbon quantum dots are used as preparation raw materials to prepare the conductive paste, so that an omnibearing conductive network with a dot line surface is formed; meanwhile, the graphene material is doped with nitrogen, so that the dispersibility of the graphene material is improved, and the conductive paste with good conductivity is finally prepared.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to graphene composite conductive slurry for a battery, and a preparation method and application thereof.
Background
Graphite plays an important role in the field of electric conduction, and along with the development of the new energy battery industry, besides the continuous attention to positive active materials, the demand of the industry for a high-performance lithium battery positive electrode material conductive agent is higher and higher, and the positive electrode material of the lithium battery often has the problem of poor electric conductivity. In the prior art, the current stable conductive agents are conductive carbon black, conductive graphite and other materials, and the conductivity of the conductive agent materials still needs to be improved, so that a novel conductive additive with better performance is found, and the problem of the positive electrode conductive agent is solved, which is particularly important.
Therefore, it is required to develop a graphene composite conductive paste for a battery, which is excellent in conductive properties.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides graphene composite conductive paste for a battery, and the conductive paste has excellent guiding performance.
The invention also provides a preparation method of the conductive paste.
The invention also provides application of the conductive paste in manufacturing electrode plates of lithium ion batteries.
The invention provides a graphene composite conductive slurry for a battery, which comprises the following preparation raw materials: a conductive agent and a dispersant;
the conductive agent comprises the following preparation raw materials:
carbon quantum dots, amino modified graphene and carboxylated carbon nanotubes;
wherein the mass ratio of the carbon quantum dots, the amino modified graphene and the carboxylated carbon nanotubes is 1: 1-2;
the preparation method of the conductive agent comprises the following steps:
preparing amino modified graphene slurry, carboxylated carbon nanotube slurry and carbon quantum dot slurry;
and mixing the amino modified graphene slurry, the carboxylated carbon nanotube slurry and the carbon quantum dot slurry, performing solid-liquid separation, collecting a solid phase, and calcining at 1000-1200 ℃ to obtain the graphene oxide/carbon quantum dot composite material.
According to at least one embodiment of the present invention, the following advantageous effects are provided:
in the conductive paste, firstly, the carboxylated carbon nanotubes, the amino modified graphene and the carbon quantum dots are prepared into paste and then mixed, and firstly, a three-dimensional network of the carboxylated carbon nanotubes and the amino modified graphene is constructed by utilizing the interaction of hydrogen bonds between the carboxylated carbon nanotubes and the amino modified graphene; the self particles of the carbon quantum dots are smaller; filling the three-dimensional network; preliminarily forming a three-dimensional network with point, line and surface contact; then calcining the slurry obtained by mixing the three components; the reduction of the carbon nano tube and the nitrogen doping of the graphene material are realized; finally forming an omnibearing conductive network of a point line surface; meanwhile, the graphene material is doped with nitrogen, so that the dispersibility of the graphene material is improved, and the conductive paste with good conductivity is finally prepared.
According to some embodiments of the invention, the mass ratio of the carbon quantum dots to the amino modified graphene is 10: 10-15.
According to some embodiments of the invention, the mass ratio of the carbon quantum dots to the carboxylated carbon nanotubes is 10: 15 to 20.
According to some embodiments of the invention, the mass ratio of the carbon quantum dots to the carboxylated carbon nanotubes is 10: 18 to 20.
According to some embodiments of the invention, the nitrogen element in the conductive agent is 0.1 to 0.5% by mass.
According to some embodiments of the invention, the nitrogen element in the conductive agent is 0.1 to 0.3% by mass.
If the nitrogen content in the conductive slurry is too high, the nitrogen content in the nitrogen-doped graphene formed after the amino modified graphene is calcined is high; the surface defects of the graphene are increased due to the fact that the nitrogen content of the graphene is too high; the graphene surface defects are increased, and although the dispersibility of the conductive paste can be improved, the conductivity of the conductive paste is adversely affected due to excessively high surface defects.
According to some embodiments of the present invention, the graphene composite conductive paste for a battery comprises the following raw materials in parts by weight:
10 parts of conductive agent and 5-10 parts of dispersant.
According to some embodiments of the present invention, the graphene composite conductive paste for a battery comprises the following raw materials in parts by weight:
10 parts of conductive agent and 5-7.5 parts of dispersant.
According to some embodiments of the present invention, the graphene composite conductive paste for a battery comprises the following raw materials in parts by weight:
10 parts of conductive agent, 5-10 parts of dispersant and 80-85 parts of water.
According to some embodiments of the present invention, the graphene composite conductive paste for a battery comprises the following raw materials in parts by weight:
10 parts of conductive agent, 5-7.5 parts of dispersant and 82.5-85 parts of water.
According to some embodiments of the invention, the dispersant comprises a nonionic dispersant and an ionic dispersant.
According to some embodiments of the invention, the non-ionic dispersant comprises at least one of PE100 (octylphenol polyoxyethylene ether), SN5040, SN5027, EFKA-4560, digao Dispers750W, digao Dispers740W, BYK190, BYK191, hydroxyethylcellulose, ethylene glycol, polyethylene glycol, polypropylene glycol, absolute ethanol, and polyacrylic acid.
According to some embodiments of the invention, the ionic dispersant comprises at least one of sodium carboxymethyl cellulose and ammonium carboxymethyl cellulose.
According to some embodiments of the present invention, the method for preparing amino-modified graphene comprises the following steps:
oxidizing and dispersing graphene to prepare a graphene oxide dispersion liquid; adding N- (2-hydroxypropyl) ethylenediamine into the graphene oxide dispersion liquid for reaction to obtain the graphene oxide dispersion liquid;
wherein the mass ratio of the graphene to the N- (2-hydroxypropyl) ethylenediamine is 1.
According to some embodiments of the invention, the oxidation is by a hummer method.
According to some embodiments of the invention, the hummer method comprises the steps of:
A. adding 2 parts of graphene and 1 part of sodium nitrate into 46 parts of concentrated sulfuric acid, and stirring in an ice bath;
B. adding 6 parts of potassium permanganate, keeping the temperature of a water bath at 35 ℃, and stirring for 4 hours;
C. adding 80 parts of water, heating the water bath to 92 ℃, continuing to heat for 2 hours, continuing to add 20 parts of water, dropwise adding hydrogen peroxide to neutralize unreacted potassium permanganate, and adding a hydrochloric acid solution after reacting for 15 min;
D. and (3) washing, namely dispersing the washed graphite oxide in water, stripping for 40min by ultrasonic oscillation, and centrifuging for 30min to obtain the graphite oxide.
According to some embodiments of the invention, the graphene has a sheet diameter of 1 μm to 15 μm.
According to some embodiments of the invention, the graphene has a sheet diameter of 2 μm to 12 μm.
According to some embodiments of the invention, the graphene has a sheet diameter of 3 to 9 μm.
According to some embodiments of the invention, the graphene has a thickness < 10nm.
According to some embodiments of the invention, the graphene oxide dispersion has a mass concentration of 5mg/mL to 10mg/mL.
According to some embodiments of the invention, the temperature of the reaction is between 50 ℃ and 120 ℃.
According to some embodiments of the invention, the reaction time is between 2h and 5h.
According to some embodiments of the invention, the number of layers of graphene is < 10.
According to some embodiments of the invention, the number of layers of graphene is 1 to 6.
According to some embodiments of the invention, the number of layers of graphene is 3 to 6.
According to some embodiments of the invention, the graphene has a specific surface area of 20m 2 /～200m 2 /g。
According to some embodiments of the invention, the graphene has a specific surface area of 25m 2 /～100m 2 /g。
According to some embodiments of the invention, the graphene has a specific surface area of 25m 2 /～50m 2 /g。
According to some embodiments of the invention, the graphene has a specific surface area of 25m 2 /～40m 2 /g。
According to some embodiments of the invention, a method of making carboxylated carbon nanotubes comprises the steps of: adding the carbon nano tube into the mixed acid solution to obtain the carbon nano tube;
wherein the mixed acid solution consists of a sulfuric acid solution and a nitric acid solution.
According to some embodiments of the invention, the mass fraction of the sulfuric acid solution is 95% to 98%.
According to some embodiments of the invention, the nitric acid solution is 65% to 70% by weight.
According to some embodiments of the invention, the weight ratio of the sulfuric acid solution, the nitric acid solution and the carbon nanotubes is 70-90: 15-5.
According to some embodiments of the invention, the carbon nanotubes are multi-walled carbon nanotubes.
According to some embodiments of the invention, the carbon nanotubes have a tube diameter of 1nm to 30nm.
According to some embodiments of the invention, the carbon nanotubes have a tube diameter of 15nm to 30nm.
According to some embodiments of the invention, the carbon nanotubes have a tube diameter of 20nm to 30nm.
According to some embodiments of the invention, the carbon nanotubes have a length of 1 μm to 40 μm.
According to some embodiments of the invention, the carbon nanotubes have a length of 5 μm to 40 μm.
According to some embodiments of the invention, the carbon nanotubes have a length of 10 μm to 40 μm.
According to some embodiments of the invention, the carbon nanotubes have a length of 10 μm to 30 μm.
The carboxylated carbon nanotubes and the amino graphene are matched for use, so that a better conductive network is formed, and the conductive performance is improved.
According to some embodiments of the invention, the carbon quantum dots have a radial dimension of 2nm to 20nm.
According to some embodiments of the invention, the carbon quantum dots have a radial dimension of 5nm to 20nm.
The second aspect of the present invention provides a preparation method of the graphene composite conductive paste for a battery, including the following steps:
and adding the conductive agent into a dispersing agent for dispersing to obtain the conductive agent.
According to at least one embodiment of the present invention, the following advantageous effects are provided:
the conductive paste with low viscosity and high conductivity is prepared by fully dispersing the conductive agent in the dispersing agent.
The third aspect of the invention provides an application of the conductive paste in preparation of an electrode plate of a lithium ion battery.
According to the invention, amino modified graphene, carboxylated carbon nanotubes and carbon quantum dots are used as preparation raw materials, a conductive agent is prepared after calcination, and then the conductive agent is subjected to calcination and dispersion treatment to prepare the high-dispersion graphene composite conductive slurry, the conductive slurry is easy to disperse and fully fills pores among battery active materials, a high-efficiency three-dimensional conductive network is formed in a pole piece, and Li in the battery charging and discharging process is accelerated + And the transmission speed of electrons, the rate capability, the cycle performance and the safety performance of the lithium ion battery are obviously improved, the industrial production can be realized, and the application prospect is wide.
Detailed Description
The idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The preparation method of the carbon quantum dots in the embodiment of the invention comprises the following steps:
mixing starch and activated carbon (Xilonggao chemical Co., ltd.) according to a mass ratio of 7:3, adding the mixture into a planetary ball mill for mechanical grinding at a grinding speed of 300rpm for 24h;
dispersing the mixed powder obtained by grinding into deionized water to obtain a carbon quantum dot/starch dispersion liquid;
dissolving the dispersion in 1mol/L hydrochloric acid to completely dissolve starch;
centrifuging at 15000rpm for at least 2 times, removing supernatant, and dialyzing the precipitate in a dialysis bag with cut-off molecular weight of 10000;
freeze-drying the dialyzed suspension to obtain a suspension with a specific surface area of 1151m 2 A carbon quantum dot with a radial dimension of 5nm to 20nm and a purity of 99.5 percent.
Example 1
The embodiment is a graphene composite conductive paste for a battery and a preparation method thereof.
The conductive paste in the embodiment is prepared from the following raw materials in parts by weight:
10 parts of conductive agent, 6.5 parts of dispersant (sodium carboxymethyl cellulose and 1.0 part of ethanol) and 82.5 parts of water.
The conductive agent in the embodiment is prepared from the following preparation raw materials in parts by weight:
1 part of carbon quantum dots, 1 part of amino modified graphene and 1 part of carboxylated carbon nanotubes.
The preparation method of the conductive agent in the embodiment includes the following steps:
s1, adding amino modified graphene into 20 parts of water, and dispersing for 0.5h at 1500rmp to obtain an amino modified graphene dispersion liquid;
adding the carboxylated carbon nanotubes into 20 parts of water, and dispersing for 0.5h at 1500rmp to prepare a carboxylated carbon nanotube dispersion liquid;
adding the carbon quantum dots into 20 parts of water, and dispersing for 0.5h under 1500rmp to prepare a carbon quantum dot dispersion liquid;
s2, mixing the amino modified graphene dispersion liquid, the carboxylated carbon nanotube dispersion liquid and the carbon quantum dot dispersion liquid, dispersing for 1h at 1500rmp, centrifuging, collecting a solid phase, and freeze-drying; calcining for 10 hours at 1200 ℃ in the argon atmosphere to obtain the conductive agent.
The nitrogen content in the conductive agent was measured to be 0.1% by an elemental analyzer.
The preparation method of the amino-modified graphene in the embodiment includes the following steps:
adding 0.2 part of N- (2-hydroxypropyl) ethylenediamine into the graphene oxide dispersion liquid, and reacting at 120 ℃ for 2 hours;
the preparation method of the graphene oxide dispersion liquid comprises the following steps:
s1, adding 2 parts of graphene and 1 part of sodium nitrate into 46 parts of concentrated sulfuric acid, and stirring in an ice bath;
s2, adding 6 parts of potassium permanganate, keeping the temperature of a water bath at 35 ℃, and stirring for 4 hours;
s3, adding 80 parts of water, heating the water bath to 92 ℃, continuing to heat for 2 hours, continuing to add 20 parts of water, dropwise adding hydrogen peroxide until no bubbles are generated, and then adding a hydrochloric acid solution (the mass fraction is 5%);
and S4, washing, namely dispersing the washed graphene oxide in water, carrying out ultrasonic oscillation stripping for 40min, centrifuging for 30min, and controlling the mass concentration of the graphene oxide dispersion liquid to be 5mg/mL.
The preparation method of the carboxylated carbon nanotube in the embodiment of the invention comprises the following steps:
s1, slowly adding 90 parts of concentrated sulfuric acid (the mass fraction is 98%) into 5 parts of concentrated nitric acid (the mass fraction is 68%), cooling to room temperature (25 ℃), and obtaining a mixed acid solution.
S2, adding 5 parts of carbon nano tubes into the mixed acid solution, reacting for 5 hours at 80 ℃, and performing centrifugal dispersion; washing to obtain the product.
In the embodiment, the graphene is selected from JY-GP01 of the New Hunan Jinyang alkene carbon New Material Co; the sheet diameter of the graphene is 3-9 mu m, the thickness is less than 10nm, the number of layers is 3-6, and the specific surface area is 25m 2 /g～31m 2 /g。
In the embodiment, the carbon nanotubes are selected from An Naiji chemical A60023, and the particle size of the carbon nanotubes is 10nm to 20nm; the length is 10-30 μm;the specific surface area is more than 150m 2 (iv) g; multi-walled carbon nanotubes.
In this embodiment, the radial size of the carbon quantum dots is 5nm to 20nm.
The preparation method of the conductive paste in the embodiment comprises the following steps:
mixing the conductive agent, the dispersing agent and water, dispersing and shearing for 0.5h at the stirring speed of 1500rmp, and carrying out nano grinding on the mixture until the fineness is less than 5 mu m to obtain the conductive slurry.
Example 2
The embodiment is a graphene composite conductive paste for a battery and a preparation method thereof.
The difference between this embodiment and embodiment 1 is:
the conductive agent in the embodiment is prepared from the following preparation raw materials in parts by weight:
1 part of carbon quantum dots, 1 part of amino modified graphene and 2 parts of carboxylated carbon nanotubes.
Example 3
The embodiment is a graphene composite conductive paste for a battery and a preparation method thereof.
The difference between this embodiment and embodiment 1 is that:
the conductive agent in the embodiment is prepared from the following preparation raw materials in parts by weight:
1 part of carbon quantum dots, 2 parts of amino modified graphene and 1 part of carboxylated carbon nanotubes.
The nitrogen content in the conductive agent was measured to be 0.14% by an elemental analyzer.
Example 4
The embodiment is a graphene composite conductive paste for a battery and a preparation method thereof.
The difference between this embodiment and embodiment 1 is that:
in the preparation method of the amino-modified graphene in this embodiment, the mass ratio of N- (2-hydroxypropyl) ethylenediamine to graphene is 0.2; the nitrogen content in the conductive agent was measured to be 0.3% by an elemental analyzer.
Comparative example 1
The comparative example is a graphene composite conductive paste for a battery and a preparation method thereof.
The difference between this embodiment and embodiment 1 is that:
in the preparation method of the amino modified graphene, the mass ratio of the N- (2-hydroxypropyl) ethylenediamine to the graphene is 0.5: 1; the nitrogen content in the conductive agent was measured to be 0.6% by an elemental analyzer.
Comparative example 2
The comparative example is a graphene composite conductive paste for a battery and a preparation method thereof.
The comparative example differs from example 1 in that: the carbon nanotubes were replaced with a60022 of An Naiji chemistry.
In the comparative example, A60022, the particle size of the carbon nano tube is 8 nm-15 nm; a length of about 50 μm; specific surface area is more than 140m 2 (iv) g; multi-walled carbon nanotubes.
Comparative example 3
The comparative example is a graphene composite conductive paste for a battery and a preparation method thereof.
The comparative example differs from example 1 in that: the carbon nanotubes were replaced with An Naiji chemical a60018.
In this comparative example, the particle size of the carbon nanotube is 30nm to 80nm; the length is less than 10 mu m; specific surface area > 60m 2 (ii)/g; multi-walled carbon nanotubes.
Comparative example 4
The comparative example is a graphene composite conductive paste for a battery and a preparation method thereof.
The comparative example differs from example 1 in that: the graphene is replaced by JY-GP50 of the new Hunan Jinyang alkene carbon material Co.
In the comparative example, the number of graphene layers is 10 to 20; the sheet diameter is 8-14 μm; the specific surface area is 22m 2 /g～28m 2 /g。
Comparative example 5
The comparative example is a graphene composite conductive paste for a battery and a preparation method thereof.
The comparative example differs from example 1 in that:
the graphene in this comparative example was not subjected to the amino modification treatment.
Comparative example 6
The comparative example is a graphene composite conductive paste for a battery and a preparation method thereof.
The comparative example differs from example 1 in that:
the carbon nanotubes in this comparative example were not carboxylated.
Comparative example 7
The comparative example is a graphene composite conductive paste for a battery and a preparation method thereof.
The comparative example differs from example 1 in that:
in this comparative example, the carbon nanotubes were not subjected to the carboxylation modification treatment and the graphene was not subjected to the amino modification treatment.
Comparative example 8
The comparative example is a graphene composite conductive paste for a battery and a preparation method thereof.
The comparative example differs from example 1 in that:
in the preparation process of the conductive paste: grinding the nano particles to the fineness of 5-10 mu m.
The electrical property test method of the invention is as follows: after the conductive slurry is uniformly dispersed, a film is coated by 50um thickness by using an automatic coating machine, and is dried, and then the conductivity of the dry film is tested by using four probes.
The results of the performance tests of the conductive pastes prepared in examples 1 to 4 of the present invention and comparative examples 1 to 8 are shown in Table 1.
Table 1 results of performance tests in conductive pastes prepared in examples 1 to 4 of the present invention and comparative examples 1 to 8
| Performance of | Electrical conductivity of | Viscosity of the oil |
| Example 1 | 1060s/cm | 1112mPa·s |
| Example 2 | 1120s/cm | 1132mPa·s |
| Example 3 | 1230s/cm | 1157mPa·s |
| Example 4 | 1130s/cm | 1037mPa·s |
| Comparative example 1 | 910s/cm | 1023mPa·s |
| Comparative example 2 | 920s/cm | 1220mPa·s |
| Comparative example 3 | 850s/cm | 1265mPa·s |
| Comparative example 4 | 840s/cm | 1180mPa·s |
| Comparative example 5 | 490s/cm | 1832mPa·s |
| Comparative example 6 | 510s/cm | 1712mPa·s |
| Comparative example 7 | 320s/cm | 1923mPa·s |
| Comparative example 8 | 830s/cm | 1358mPa·s |
The difference between example 2 and example 1 is that: the dosage of the carboxylated carbon nano tube is increased; the formation of a conductive network is further promoted by increasing the using amount of the carboxylated carbon nano tube, so that the conductivity of the slurry is improved; while the viscosity is slightly increased.
The difference between example 3 and example 1 is that: the using amount of the amino modified graphene is increased, and the formation of a conductive network is further promoted by increasing the using amount of the amino modified graphene, so that the conductivity of the slurry is improved; while the viscosity is slightly increased.
The difference between example 4 and example 1 is that: the nitrogen content in the conductive agent is increased, and the dispersibility of the conductive agent is improved, so that the conductivity of the conductive paste is improved; meanwhile, the viscosity of the conductive paste is reduced.
The difference between comparative example 1 and example 1 is that: in the comparative example 1, the nitrogen content in the conductive agent is increased, and the conductive performance is reduced; the nitrogen doping amount is too high, so that the defect concentration of the graphene is too high, and the conductivity is reduced.
The difference between comparative example 2 and example 1 is that: comparative example 2, the carbon nanotubes are too long, and the conductivity is reduced; therefore, the carbon nanotubes have an excessively long length, resulting in poor contact with other conductive particles during the formation of a conductive network, thereby resulting in poor conductive performance.
The difference between comparative example 3 and example 1 is that: the grain diameter of the carbon nano tube is larger in the comparative example 3, and the conductivity is reduced; therefore, the carbon nanotubes have a large particle size, which results in large voids inside the carbon nanotubes, which is not favorable for forming a conductive network of a dot-line surface, resulting in poor conductivity.
The difference between comparative example 4 and example 1 is that: in the comparative example 4, the number of graphene layers is increased, and the conductivity is reduced; therefore, under the condition that the number of graphene layers is increased, the graphene is stacked seriously, and a conductive network of a point line surface is not formed, so that the conductivity is poor.
The difference between comparative example 5 and example 1 is that: in the comparative example 5, the conductivity of the graphene is reduced without performing amino modification treatment; therefore, under the condition that the graphene is not subjected to amino modification, the graphene has a poor dispersion effect, and is not beneficial to forming a conductive network of a point-line surface, so that the conductivity is poor.
The difference between comparative example 6 and example 1 is that: in the comparative example 6, the carbon nanotubes are not carboxylated, and the conductivity is reduced; therefore, on the basis that the carbon nano tube is not subjected to carboxylation modification, the carbon nano tube and the amino modified graphene are not favorable for forming a conductive network with a point line surface, so that the conductive performance is poor.
The difference between comparative example 7 and example 1 is that: in comparative example 7, the carbon nanotubes are not subjected to carboxylation modification treatment and the graphene is not subjected to amino modification treatment, so that the conductivity is reduced; therefore, on the basis that the graphene is not subjected to amino modification and the carbon nanotube is not subjected to carboxylation modification, the graphene has a poor dispersion effect, and is not beneficial to forming a conductive network of a point-line surface, so that the conductivity is poor.
The difference between comparative example 8 and example 1 is that: in the comparative example 8, the conductive paste has the fineness of 5-10 μm, and the conductivity is reduced; the fineness of the conductive paste is too large, so that the dispersion effect of the conductive agent is poor, and the conductivity and viscosity of the conductive paste are affected.
In summary, in the conductive paste of the present invention, the carboxylated carbon nanotubes, the amino-modified graphene and the carbon quantum dots are first prepared into a paste and then mixed, and a three-dimensional network of the carboxylated carbon nanotubes and the amino-modified graphene is first constructed by utilizing the interaction of hydrogen bonds between the carboxylated carbon nanotubes and the amino-modified graphene; the self particles of the carbon quantum dots are smaller; filling the three-dimensional network; preliminarily forming a three-dimensional network with point, line and surface contact; then calcining the slurry obtained by mixing the three components; the reduction of the carbon nano tube and the nitrogen doping of the graphene material are realized; finally forming an omnibearing conductive network of a point line surface; meanwhile, the graphene material is doped with nitrogen, so that the dispersibility of the graphene material is improved, and the conductive paste with good conductivity is finally prepared.
While the embodiments of the present invention have been described in detail with reference to the specific embodiments, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
Claims (8)
1. The utility model provides a graphite alkene composite conduction thick liquids for battery which characterized in that: the method comprises the following preparation raw materials: a conductive agent and a dispersant; the fineness of the conductive slurry is less than 5 mu m;
the conductive agent comprises the following preparation raw materials:
carbon quantum dots, amino modified graphene and carboxylated carbon nanotubes;
wherein the mass ratio of the carbon quantum dots, the amino modified graphene and the carboxylated carbon nanotubes is 1:1 to 2:1 to 2;
the preparation method of the conductive agent comprises the following steps:
preparing amino modified graphene slurry, carboxylated carbon nanotube slurry and carbon quantum dot slurry;
mixing the amino modified graphene slurry, the carboxylated carbon nanotube slurry and the carbon quantum dot slurry, performing solid-liquid separation, collecting a solid phase, and calcining at 1000-1200 ℃ to obtain the modified graphene nano-tube slurry;
the preparation method of the amino modified graphene comprises the following steps:
oxidizing and dispersing graphene to prepare a graphene oxide dispersion liquid; adding N- (2-hydroxypropyl) ethylenediamine into the graphene oxide dispersion liquid for reaction to obtain the graphene oxide dispersion liquid;
wherein the mass ratio of the graphene to the N- (2-hydroxypropyl) ethylenediamine is 1;
the number of layers of the graphene is less than 10.
2. The graphene composite conductive paste for a battery according to claim 1, wherein: the preparation method comprises the following raw materials in parts by weight:
10 parts of conductive agent and 5-10 parts of dispersant.
3. The graphene composite conductive paste for a battery according to claim 1, wherein: the reaction temperature is 50-120 ℃.
4. The graphene composite conductive paste for a battery according to claim 1, wherein: the preparation method of the carboxylated carbon nanotube comprises the following steps: adding the carbon nano tube into the mixed acid solution to obtain the carbon nano tube;
wherein the mixed acid solution is a mixed solution of sulfuric acid and nitric acid.
5. The graphene composite conductive paste for a battery according to claim 1, wherein: the radial size of the carbon quantum dots is 5 nm-20 nm.
6. A method of preparing the graphene composite conductive paste for a battery according to any one of claims 1 to 5, wherein: the method comprises the following steps:
adding the conductive agent into a dispersing agent for dispersion, and grinding to obtain the conductive agent;
the fineness of the particles in the ground slurry is less than 5 mu m.
7. The method of claim 6, wherein: the dispersed rotating speed is 1000 rmp-2000 rmp; the dispersing time is 0.5-2 h.
8. Use of the graphene composite conductive paste for batteries according to any one of claims 1 to 5 in the preparation of electrode sheets of lithium ion batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210359191.5A CN114665096B (en) | 2022-04-07 | 2022-04-07 | Graphene composite conductive slurry for battery and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210359191.5A CN114665096B (en) | 2022-04-07 | 2022-04-07 | Graphene composite conductive slurry for battery and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114665096A CN114665096A (en) | 2022-06-24 |
| CN114665096B true CN114665096B (en) | 2022-11-22 |
Family
ID=82035487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210359191.5A Active CN114665096B (en) | 2022-04-07 | 2022-04-07 | Graphene composite conductive slurry for battery and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114665096B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104766645A (en) * | 2015-03-24 | 2015-07-08 | 中国石油大学(北京) | Carbon nanotube-graphene composite electric conduction slurry and preparation method and application thereof |
| CN106711453A (en) * | 2016-12-28 | 2017-05-24 | 深圳市德方纳米科技股份有限公司 | Conductive carbon slurry, cathode material pole piece and lithium ion battery |
| CN109244422A (en) * | 2018-10-19 | 2019-01-18 | 中国矿业大学 | A kind of lithium ion battery SnS/ carbon quantum dot/graphene composite negative and preparation method |
| CN110193358A (en) * | 2019-06-27 | 2019-09-03 | 中素新科技有限公司 | Composite sponge and its preparation method and application containing amino modified graphene |
| CN110620237A (en) * | 2019-10-25 | 2019-12-27 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| CN111151765A (en) * | 2020-01-20 | 2020-05-15 | 西安稀有金属材料研究院有限公司 | Preparation method of three-dimensional structure nano carbon material reinforced copper-based composite material |
| CN111470491A (en) * | 2020-04-13 | 2020-07-31 | 北京石墨烯研究院有限公司 | Carbon hybrid powder and preparation method thereof |
| CN112210120A (en) * | 2020-10-10 | 2021-01-12 | 吉林大学 | Heat-conducting filler and preparation method thereof, and polyarylethersulfone heat-conducting composite material and preparation method thereof |
| CN112687865A (en) * | 2020-12-25 | 2021-04-20 | 惠州亿纬锂能股份有限公司 | Lithium ion battery cathode slurry, preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9129732B2 (en) * | 2013-07-09 | 2015-09-08 | National Taipei University Of Technology | Magnetorheological fluid composition and method for forming the same |
| CN104975368B (en) * | 2015-07-27 | 2017-04-12 | 天津工业大学 | Multiwalled carbon nanotube and graphene reinforced modified regenerated protein fiber and preparation method thereof |
| CN105842307A (en) * | 2016-03-15 | 2016-08-10 | 南京理工大学 | High-sensitivity phenol electrochemical sensor and preparation method thereof |
| KR20190112954A (en) * | 2018-03-27 | 2019-10-08 | 한국에너지기술연구원 | High capacity aluminum secondary battery and method for manufacturing thereof |
| CN110660957B (en) * | 2018-12-29 | 2020-12-04 | 宁德时代新能源科技股份有限公司 | Electrode plate and electrochemical device |
-
2022
- 2022-04-07 CN CN202210359191.5A patent/CN114665096B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104766645A (en) * | 2015-03-24 | 2015-07-08 | 中国石油大学(北京) | Carbon nanotube-graphene composite electric conduction slurry and preparation method and application thereof |
| CN106711453A (en) * | 2016-12-28 | 2017-05-24 | 深圳市德方纳米科技股份有限公司 | Conductive carbon slurry, cathode material pole piece and lithium ion battery |
| CN109244422A (en) * | 2018-10-19 | 2019-01-18 | 中国矿业大学 | A kind of lithium ion battery SnS/ carbon quantum dot/graphene composite negative and preparation method |
| CN110193358A (en) * | 2019-06-27 | 2019-09-03 | 中素新科技有限公司 | Composite sponge and its preparation method and application containing amino modified graphene |
| CN110620237A (en) * | 2019-10-25 | 2019-12-27 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| CN111151765A (en) * | 2020-01-20 | 2020-05-15 | 西安稀有金属材料研究院有限公司 | Preparation method of three-dimensional structure nano carbon material reinforced copper-based composite material |
| CN111470491A (en) * | 2020-04-13 | 2020-07-31 | 北京石墨烯研究院有限公司 | Carbon hybrid powder and preparation method thereof |
| CN112210120A (en) * | 2020-10-10 | 2021-01-12 | 吉林大学 | Heat-conducting filler and preparation method thereof, and polyarylethersulfone heat-conducting composite material and preparation method thereof |
| CN112687865A (en) * | 2020-12-25 | 2021-04-20 | 惠州亿纬锂能股份有限公司 | Lithium ion battery cathode slurry, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114665096A (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Preparation and application of iron oxide/graphene based composites for electrochemical energy storage and energy conversion devices: Current status and perspective | |
| CN113035407B (en) | Carbon nano tube compound conductive slurry for lithium ion battery and preparation method thereof | |
| CN110970620B (en) | Preparation method of high-stability graphene/carbon nanotube composite conductive slurry | |
| Jiang et al. | Ultrafine SnO2 in situ modified graphite felt derived from metal–organic framework as a superior electrode for vanadium redox flow battery | |
| WO2016090958A1 (en) | Preparation method for mixed capacitor negative electrode slurry | |
| CN110112408A (en) | A kind of graphene-silicon composite and preparation method thereof, electrode material and battery | |
| Yang et al. | Ionic-liquid-bifunctional wrapping of ultrafine SnO 2 nanocrystals into N-doped graphene networks: high pseudocapacitive sodium storage and high-performance sodium-ion full cells | |
| CN109728301B (en) | Graphene-containing lithium battery conductive slurry and preparation method thereof | |
| Wu et al. | Self-assembled graphene-wrapped SnO2 nanotubes nanohybrid as a high-performance anode material for lithium-ion batteries | |
| Han et al. | Facile assembly of α-Fe2O3 nanorings@ reduced graphene oxide composites with high lithium storage performance | |
| Tang et al. | Fabrication of a highly stable Nb 2 O 5@ C/CNTs based anolyte for lithium slurry flow batteries | |
| CN106374086A (en) | Nano lithium titanate-graphene composite material and preparation method therefor | |
| CN109909511B (en) | Preparation method and application of bismuth-based hollow nano material | |
| KR20170122202A (en) | Use of a liquid composition of carbon-based nanofillers for lead battery electrode formulations | |
| Rajagopalan et al. | Redox synthesis of poly (p–phenylenediamine)–reduced graphene oxide for the improvement of electrochemical performance of lithium titanate in lithium–ion battery anode | |
| CN114665096B (en) | Graphene composite conductive slurry for battery and preparation method and application thereof | |
| US20140170491A1 (en) | Mesoporous starburst carbon incorporated with metal nanocrystals or metal oxide nanocrystals, and uses thereof | |
| CN109935843B (en) | Method for uniformly distributing PTFE (polytetrafluoroethylene) binder and electrode key component material and application of PTFE binder and electrode key component material in battery industry | |
| CN115084528A (en) | Preparation method and application of carbon-coated metal foil | |
| CN111533115B (en) | High-capacity high-cycle-efficiency silicon-based/graphene nanoribbon composite material and preparation method thereof | |
| Mkhondo et al. | Surface properties of metal oxides and their role on electrochemical hydrogen storage of carbon nanotubes | |
| CN114976022B (en) | Graphene composite dry powder conductive agent and preparation method and application thereof | |
| Palas et al. | Electrochemical performance of reduced graphene oxide-silica composite in polyaniline | |
| CN113782734B (en) | Preparation method of silicon monoxide negative pole piece | |
| Meng et al. | Fe2O3 nanoparticles anchored on thermally oxidized graphene for boosting lithium storage properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 410000 No. 7, Pingtou North Road, Liuyang high tech Industrial Development Zone, Changsha City, Hunan Province Applicant after: Hunan Jinyang alkene carbon new material Co.,Ltd. Address before: 410000 No. 7, Pingtou North Road, Liuyang high tech Industrial Development Zone, Changsha City, Hunan Province Applicant before: Hunan Jinyang New Carbon Material Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |